Methods and compositions to protect asphaltic materials

ABSTRACT

Asphaltic materials are provided with increased resistance to damage from water, oil and weather by a process which comprises treating said materials with an aqueous composition containing: (A) from about 0.1 to 4% by weight, on a 100% solids basis, of an aqueous solution or self-dispersed emulsion or dispersion of a copolymer which is a reaction product of monomers containing fluorinated groups, cationic groups and nonionic groups, optionally (B) an effective amount of a penetration assistant, and (C) water to make up 100%.

This application is a provision of Ser. No. 60/099,699 filed Sep. 10,1998.

The present invention relates to methods and compositions to protectasphaltic materials from water, oil and weather damage. Moreparticularly it relates to methods and compositions which compriseapplying certain cationic fluorochemical copolymer compositions toasphaltic material such as an asphaltic traffic-bearing surface orroofing material to protect the asphaltic material from such damage.

BACKGROUND OF THE INVENTION

The terms asphalt and bitumen are often used synonymously in the U.S. torefer to a generic class of amorphous, dark-colored thermoplasticmaterials composed principally of high molecular weight hydrocarbons.The primary source of asphalt is petroleum oil, where it is obtained asthe heavy residue which remains after the volatile gasoline and oilcomponents have been removed by distillation.

Asphalt serves primarily as a binder in mixtures of asphalt and mineralaggregates which are employed in the construction of roads and similartraffic-bearing surfaces such as driveways, parking areas and airportrunways. As such it generally comprises 4 to 10 weight percent of themixture, which is sufficient to coat the mineral aggregate. Asphalticroad paving material is sometimes also referred to as asphalt or"blacktop". According to the review article "Asphalt and Bitumin" byCorbett and Urban in Ullmann's Encyclopedia of Industrial Chemistry,Fifth Ed. (1985), Vol. A3, pages 169-188, over 90% of alltraffic-bearing areas are constructed with asphalt mixes.

Although asphaltic traffic-bearing areas are compacted by hot rolling,they are still more porous than surfaces of concrete. There is also anupper layer of asphalt-coated aggregate which is directly exposed tosunlight, air, temperature extremes, rain, snow, ice, vehicle exhaustemissions and fluid leaks (primarily engine oil but also gasoline,diesel fuel and antifreeze solutions), and salts used to dissolve snowand/or ice. Additionally, airport traffic-bearing surfaces are exposedto aviation fuel spills, hot jet engine exhaust and, in cold weather, toaircraft deicing fluids. A major problem in cold climates is freeze-thawdamage from ice, but all of the above exposures lead to degradation ofasphaltic traffic-bearing materials. As a result a huge amount of moneyis expended each year to repair or resurface such materials. Thus thereis a clear need for a cost-effective way of extending the usefullifetime of asphaltic traffic-bearing areas.

Asphalt is also used in roofing materials. Asphalt composition shingles,which are used as roofing materials on more than 95% of privatedwellings in North America according to the above-mentioned Ullmann'sarticle, consist of a glass fiber or cellulosic backing coated on bothsides with a filled asphalt and surfaced on the weather surface withmineral granules. The filed asphalt serves as a binder for both thebacking material and the mineral granules. Asphalt is also used as boththe binder and upper surface of single and multilayer roofing systems.These asphaltic weather surfaces are subjected to many of the sameexposures as a roadway, that is, sunlight, air, temperature extremes,rain, snow and freeze-thaw damage from ice, and eventually replacementis required. A cost-effective way of extending the useful lifetime ofasphalt composition shingles and other asphaltic roofing surfaces wouldtherefore also be highly desirable.

It is known that fluorochemicals, particularly certain fluorochemicalcopolymers, can be used to impart water, oil or grease repellency topaper and paper products, and to textile fibers such as nylon used incarpets and upholstered furniture. It is also known that certainfluorochemical copolymers can be used in combination with othersubstances to improve the resistance of certain construction materialsto water and oil damage. For example JP 9286676 A teaches to employ anaqueous emulsion of a fluororesin which is a copolymer of afluoro-olefin, a carboxylic acid vinyl ester and unsaturated monomershaving hydrophilic functional groups with a water emulsion of a silanecompound which has hydrolyzable functional groups to form awater-repellent, weather-resistant coating on the surface of curedconcrete.

EP-A 0 714 921 teaches two component resin compositions forwater-repellent coatings for textiles and building materials whichcomprise a fluorinated acrylic copolymer component which also containscationic amino groups, either in salt or quaternized form, and otherfunctional groups, and a polyisocyanate component. On mixing the twowater-based components and applying the mixture to building materials,they harden rapidly to a coating which imparts stable water- andoil-repellent, anti-graffiti properties to the treated substrates.

U.S. Pat. No. 5,753,569 teaches a two component coating treatment torender substrates selected from the group consisting of naturallyoccurring and synthetic textiles and their mixtures, leather, mineralsubstances, thermoplastic and thermosetting polymers and paper, oil-,water- and soil-repellent by applying thereto compositions containingcomponents A and B, wherein component B is a fluorine-freepoly(meth)acrylate ester and component A is fluorine-containing andcomprises repeating units from a) 40 to 85% by weight of (meth)acrylatescontaining perfluoroalkyl groups, b) 1 to 45% by weight of one or moremonomers from the group consisting of styrene, acrylonitrile, vinylacetate, vinyl propionate and (meth)acrylate esters, c) 4 to 30% byweight of (meth)acrylate esters of polyether polyols and d) 1 to 15% byweight of ionic or ionizable monomers which contain either an amino or acarboxyl function.

EP-A 0 714 870 teaches an oleophobic and hydrophobic treatment forcertain construction materials which comprises applying to the surfaceof the materials to be treated a mixture of a water soluble cationicfluorinated acrylic copolymer of the type disclosed in U.S. Pat. No.5,493,998 and a polymeric film former, polyvinyl alcohol. The copolymersare reaction products of a perfluoroalkylethyl acrylate, adialkylalkylaminoethyl methacrylate, vinyl acetate and optionally afourth monomer such as butyl methacrylate. While some protection can beprovided by saturating a surface with an aqueous solution of thecopolymer alone, the high concentration of the water-soluble cationicfluorinated acrylic copolymer required, 20-25%, makes this approachunattractive and impractical.

None of the above-mentioned references teach how to protect an asphalticsurface. Additionally, all of the above surface treatments, whether theyemploy cross-linked resins or physical mixtures with a polymeric filmformer, form coatings which seal the surface of the substrate. Apartfrom the esthetically undesirable shiny and unnatural appearance, acoating will normally make a surface more slippery and prevent waterdrainage. These properties would be highly undesirable in a surfacetreatment for asphaltic traffic-bearing areas such as driveways, parkingareas, roadways and airport runways for example, and one skilled in theart would avoid such coatings. They would also be ruled out for use onasphalt composition shingles on esthetic grounds.

It was therefore and object of this invention to find a one componentsurface treatment for asphaltic materials which was free of crosslinkingagents and fluorine-free film-forming polymers, which would not impart ashiny and unnatural appearance to treated surfaces, would not impairtraction on treated traffic bearing areas and which would extend theuseful lifetime of the asphaltic materials by providing protection toasphaltic materials from water, oil and weather damage.

Surprisingly, it has now been found that asphaltic materials, such astraffic bearing areas and roofing materials, can be provided withincreased resistance to damage from water, oil and weather, whileremaining porous and retaining a natural appearance, by treating themwith a composition comprising a dilute aqueous solution orself-dispersed emulsion or dispersion of certain cationic, fluorinatedcopolymers, optionally in the presence of an effective amount of apenetration assistant.

DETAILED DISCLOSURE OF THE INVENTION

The present invention comprises a composition which provides asphalticmaterials with increased resistance to damage from water, oil andweather, which composition comprises:

(A) from about 0.1 to 4% by weight, on a 100% solids basis, of anaqueous solution or self-dispersed emulsion or dispersion of a copolymerwhich is a reaction product of monomers containing fluorinated groups,cationic groups and nonionic groups, optionally

(B) an effective amount of a penetration assistant, and

(C) water to make up 100%, with the proviso that if the copolymer is areaction product of monomers which include 1% or more of vinyl acetate,the composition also contains from about 0.01 to 1% by weight of apenetration assistant.

Preferably the treating compositions comprise from about 0.2 to 2% byweight of the aqueous solution or self-dispersed emulsion or dispersionof the copolymer on a 100% solids basis, more preferably from 0.4 to 1%of the copolymer, and from about 0.01 to 1% by weight, more preferablyfrom 0.05 to 0.4% by weight of the penetration assistant.

The treating compositions may also contain up to about 2% by weight of awater-miscible organic solvent such as acetone, dioxane,tetrahydrofuran, dimethyl formamide, N-methyl-pyrrolidone,dimethylsulfoxide, ethanol, isopropanol, methyl isobutyl ketone,ethylene glycol or propylene glycol, such solvents being commonlyemployed during the synthesis of the copolymers. Additionally thepenetration assistant may be added as a solution in an organic solvent.Preferably however the treating compositions contain no or only lowamounts of organic solvents for health, safety and ecological reasons.

The treating composition may also advantageously contain conventionaladditives which are compatible with the mixture of the aqueous solutionor self-dispersed emulsion or dispersion of the copolymer and thepenetration assistant. In particular the treating composition maycontain an effective amount of a preservative such as an antimicrobial,a bactericide, a fungicide or an algicide. Many such materials andcommercial sources thereof are listed in McCutcheon's 1994 Volume 2:Functional Materials, North American Edition, McCutcheon's Division, MCPublishing Co., Glen Rock, N.J.

Component (A) suitably contains a copolymer which is a reaction productof one or more meth(acrylate) monomers containing polyfluorinated alkylgroups, cationic nitrogen groups which are partially or fullyquaternized or in the form of a salt, and nonionic groups. To obtain asatisfactory balance of hydrophobic and oleophobic properties it ispreferred that the copolymer be a reaction product of from about 60-90%by weight of one or more meth(acrylate) monomers containingpolyfluorinated alkyl groups, from about 10 to about 30% by weight ofone or more meth(acrylate) monomers containing cationic groups which arepartially or fully quaternized or in the form of a salt and from about 1to about 10% by weight of one or more monomers containing nonionicgroups.

Suitable monomers containing nonionic groups include ethylene,propylene, isobutene, chloro-3-isobutene-1, butadiene, isoprene, chloro-and dichloro-butadienes, fluoro- and difluoro-butadienes, vinylidinechloride, vinyl- or vinylidine fluoride, allyl bromide, methallylchloride, vinyl-toluene, alpha-methylstyrene, alpha-cyanomethylstyrene,divinylbenzene, N-vinyl-carbazole, methyl vinyl ketone, allyl acetate,allyl propionate, allyl isobutyrate, allyl heptanoate, cetyl vinylether, dodecyl vinyl ether, allyl-, methyl-, ethyl-, propyl-,isopropyl-, butyl-, isobutyl-, hexyl-, heptyl-, ethyl-2-hexyl-,cyclohexyl-, lauryl-, stearyl- or ethoxyethyl esters of acrylic,methacrylic, alpha-chloroacrylic, crotonic, maleic, fumaric, itaconic,citraconic and senecioic acid, glycol or polyalkyleneglycol diacrylatesand dimethacrylates, acrylonitrile, methacrylonitrile,chloro-2-acrylonitrile, cyano-2-ethyl acrylate, methyleneglutaronitrile, vinylidene cyanate, isopropyl cyanoacrylate,trisacryloyl-hexahydro-s-triazine, allyl alcohol, allyl glycolate,isobutenediol, allyloxy-ethanol, o-allylphenol, divinylcarbinol,glycerol-allyl ether, acrylamide, methacrylamide, maleamide andmaleimide, N-(cyanoethyl)acrylamide, N-isopropyl-acrylamide,diacetone-acrylamide, N-(hydroxymethyl)-acrylamide and methacrylamide,N-(alkoxymethyl)-acrylamides and methacrylamides,glyoxal-bis-acrylamide, amino-3-crotononitrile, monoallylamine,vinylpyridines, glycidyl acrylate or methacrylate and theirchlorohydrins, allyl glycidyl ether and acrolein.

Epoxy- or chlorohydrin-containing nonionic groups are preferred, withglycidyl methacrylate being especially preferred.

Said copolymers are known per se or can be prepared by the conventionalfree radical polymerization methods described in the referencesdiscussed above, which are incorporated by reference. Additionally, someof the copolymers of the references are commercially available.Typically the copolymers are prepared as aqueous solutions orself-dispersed emulsions or dispersions containing 20 to 35% by weightof the copolymer.

Preferably component (A) contains a copolymer which comprises monomerscopolymerized in the following percentages by weight, relative to thetotal weight of the copolymers:

(a) from about 60% to about 90% of at least one monomer of the formulaI:

    R.sub.f --Q--A--C(O)----C(R)═CH.sub.2                  (I)

wherein

R_(f) is a straight or branched-chain perfluoroalkyl group of from 2 toabout 20 carbon atoms,

R is H or CH₃,

A is O, S, or N(R'), wherein R' is H or an alkyl of from 1 to 4 carbonatoms,

Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 toabout 15 carbon atoms, --(C_(n) H_(2n))(OC_(q) H_(2q))_(m) --, --SO₂--NR'(C_(n) H_(2n))--, or --CONR'(C_(n) H_(2n))--, wherein R' is H or analkyl of 1 to 4 carbon atoms, n is 1 to 15, q is 2 to 4, and m is 1 to15;

(b) from about 10 to about 40% of at least one monomer of the formulaII:

    (R.sub.1).sub.2 N--CH.sub.2 CH.sub.2 --O--C(O)--C(R.sub.2)═CH.sub.2 (II)

wherein

R₁ is an alkyl group of from 1 to 3 carbon atoms,

R₂ is H or an alkyl radical of 1 to 4 carbon atoms, and wherein thenitrogen is 40 to 100% quaternized or in the form of a salt; and

(c) from about 1 to about 7% of at least one monomer of formula III orIV, or a mixture thereof: ##STR1## or

    Cl--CH.sub.2 --CH(OH)CH.sub.2 --O--C(O)----C(R.sub.4)═CH.sub.2 (IV),

wherein

R₃ and R₄ are each independently H or the same or different alkylradical of 1 to about 4 carbon atoms.

In the above compositions, preferably in formula I, R_(f) is a straightchain perfluoroalkyl group of 2 to about 20 carbon atoms, or a mixturethereof, A is O and Q is an alkylene of 1 to about 15 carbon atoms. Morepreferably the monomer of formula I is a perfluoroalkylethyl acrylatehaving the formula CF₃ CF₂ (CF₂)_(x) C₂ H₄ OC(O)--C(H)═CH₂ wherein x isan even integer from 4 to 18, or a mixture thereof. Most preferred is amixture having a perfluoroalkyl carbon chain length distribution (x) byweight of about 50% of 8-carbon, about 29% of 10-carbon, about 11% of12-carbon, and with smaller percentages of 6-carbon, 14-carbon andlonger chain lengths. Preferably the monomer of formula 11 isdiethylaminoethyl methacrylate which has undergone partial or fullsalinization or quaternization and the monomer of formula III isglycidyl methacrylate.

Preferably the proportion of the monomer of formula I in the copolymeris from about 79% to about 85% by weight, the proportion of the monomerof formula II in the copolymer (in its salt form) is from about 13% toabout 19% by weight and the proportion of the monomer of formula III orIV, or a mixture thereof, in the copolymer is from about 1% to about 5%by weight.

The above copolymers are known per se from U.S. Pat. No. 5,674,961, thedisclosure of which is incorporated by reference, where they are taughtto be useful in treating paper and paper products. They are also knownper se from U.S. Pat. No. 5,919,527, the disclosure of which isincorporated by reference, where they are taught to be useful intreating certain hard surfaces including construction materials such asbrick, stone, wood, concrete, ceramics, tile, glass, stucco, gypsumdrywall, particle board, or chip board. An especially preferredcopolymer of of the type described above is commercially available fromthe Consumer Care Division of Ciba Specialty Chemicals Corporation, HighPoint, N.C. as a 30% aqueous composition designated LODYNE P-514.

Component (B) is a penetration assistant. A penetration assistant is anysurface-active organic substance that enhances the ability of an aqueoussolution or self-dispersed emulsion or dispersion of the copolymer topenetrate and wet out an asphaltic substrate.

Suitable penetration assistants include both ionic and nonionicsurfactants. Preferably the penetration assistant is, or contains anonionic, cationic or amphoteric surfactant. The penetration assistantmay be monomeric, oligomeric or polymeric. A large number ofcommercially available surfactants are described in McCutcheon's 1994Volume 1: Emulsifiers and Detergents, North American Edition,McCutcheon's Division, MC Publishing Co., Glen Rock, N.J.

Advantageously the penetration assistant is used in liquid form, eitheras a neat liquid or as an aqueous or non-aqueous solution of the activesubstance. A particularly preferred penetration assistant is aproprietary liquid mixture known as Solvent-D, which is available fromPolypore, Inc., Tucson, Ariz. Solvent-D contains propylene carbonate assolvent.

The amount of the penetration assistant to employ can vary widely.Generally an effective amount of the penetration assistant will reducethe surface tension of water by at least 15 percent, preferably by 20 to60 percent. Advantageously the composition contains from about 0.01 to1% by weight of a penetration assistant, preferably from 0.05 to 0.4%and more preferably from 0.08 to 0.15% by weight of the penetrationassistant. These weight percentages are on an "as is" basis, meaningthat the presence or absence of a solvent or a diluent in thecommercially available material is ignored. Since the dilute aqueoussolution or self-dispersed emulsion or dispersion of the fluorochemicalcopolymer already has a substantially lower surface tension than water,the surface tension lowering effect of the penetration assistant willnormally be lower than it is with pure water.

The present invention also comprises a process which provides asphalticmaterials with increased resistance to damage from water, oil andweather, which process comprises treating said materials with an aqueouscomposition containing:

(A) from about 0.1 to 4% by weight, on a 100% solids basis, of anaqueous solution or self-dispersed emulsion or dispersion of a copolymerwhich is a reaction product of monomers containing fluorinated groups,cationic groups and optionally nonionic groups, optionally

(B) an effective amount of a penetration assistant, and

(C) water to make up 100%.

Preferably the process comprises treating above substrates with anaqueous composition which comprises from about 0.2 to 2% by weight ofthe aqueous solution or self-dispersed emulsion or dispersion of thecopolymer on a 100% solids basis, and from about 0.01 to 1% by weight ofthe penetration assistant.

In a preferred process the copolymer in (A) is a reaction product offrom about 60-90% by weight of one or more meth(acrylate) monomerscontaining polyfluorinated alkyl groups, from about 10 to about 40% byweight of one or more meth(acrylate) monomers containing cationic groupsand from about 1 to about 10% by weight of one or more monomerscontaining nonionic groups. Preferably the nonionic group is selectedfrom the group consisting of ethylene, propylene, isobutene,chloro-3-isobutene-1, butadiene, isoprene, chloro- anddichloro-butadienes, fluoro- and difluoro-butadienes, vinylidinechloride, vinyl- or vinylidine fluoride, allyl bromide, methallylchloride, vinyl-toluene, alpha-methylstyrene, alpha-cyanomethylstyrene,divinylbenzene, N-vinylcarbazole, methyl vinyl ketone, allyl acetate,allyl propionate, allyl isobutyrate, allyl heptanoate, cetyl vinylether, dodecyl vinyl ether, allyl-, methyl-, ethyl-, propyl-,isopropyl-, butyl-, isobutyl-, hexyl-, heptyl-, ethyl-2-hexyl-,cyclohexyl-, lauryl-, stearyl- or ethoxyethyl esters of acrylic,methacrylic, alpha-chloroacrylic, crotonic, maleic, fumaric, itaconic,citraconic and senecioic acid, glycol or polyalkyleneglycol diacrylatesand dimethacrylates, acrylonitrile, methacrylonitrile,chloro-2-acrylonitrile, cyano-2-ethyl acrylate, methyleneglutaronitrile, vinylidene cyanate, isopropyl cyanoacrylate,trisacryloyl-hexahydro-s-triazine, allyl alcohol, allyl glycolate,isobutenediol, allyloxy-ethanol, o-allylphenol, divinylcarbinol,glycerol-allyl ether, acrylamide, methacrylamide, maleamide andmaleimide, N-(cyanoethyl)acrylamide, N-isopropyl-acrylamide,diacetone-acrylamide, N-(hydroxymethyl)-acrylamide and methacrylamide,N-(alkoxymethyl)-acrylamides and methacrylamides,glyoxal-bis-acrylamide, amino-3-crotononitrile, monoallylamine,vinylpyridines, glycidyl acrylate or methacrylate and theirchlorohydrins, allyl glycidyl ether and acrolein. It is especiallypreferred that the nonionic monomer comprises at least one monomerselected from the group consisting of glycidyl acrylate or methacrylateand their chlorohydrins.

A particularly preferred process comprises treating above substrateswith an aqueous composition wherein the copolymer in (A) is a reactionproduct of monomers copolymerized in the following percentages byweight, relative to the total weight of the copolymers:

(a) from about 60% to about 90% of at least one monomer of the formulaI:

    R.sub.f --Q--A--C(O)----C(R)═CH.sub.2                  (I)

wherein

R_(f) is a straight or branched-chain perfluoroalkyl group of from 2 toabout 20 carbon atoms,

R is H or CH₃,

A is O, S, or N(R'), wherein R' is H or an alkyl of from 1 to 4 carbonatoms,

Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 toabout 15 carbon atoms, --(C_(n) H_(2n))(OC_(q) H_(2q))_(m) --, --SO₂--NR'(C_(n) H_(2n))--, or --CONR'(C_(n) H_(2n))--, wherein R' is H or analkyl of 1 to 4 carbon atoms, n is 1 to 15, q is 2 to 4, and m is 1 to15;

(b) from about 10 to about 40% of at least one monomer of the formulaII:

    (R.sub.1).sub.2 N--CH.sub.2 CH.sub.2 --O--C(O)--C(R.sub.2)═CH.sub.2 (II)

wherein

R₁ is an alkyl group of from 1 to 3 carbon atoms,

R₂ is H or an alkyl radical of 1 to 4 carbon atoms, and wherein thenitrogen is 40 to 100% quaternized or in the form of a salt; and

(c) from about 1 to about 7% of at least one monomer of formula III orIV, or a mixture thereof: ##STR2## or

    Cl--CH.sub.2 --CH(OH)CH.sub.2 --O--C(O)----C(R.sub.4)═CH.sub.2 (IV)

wherein

R₃ and R₄ are each independently H or the same or different alkylradical of 1 to about 4 carbon atoms.

In the above process preferably R_(f) is a straight chain perfluoroalkylgroup of 2 to about 20 carbon atoms, or a mixture thereof, A is O and Qis an alkylene of 1 to about 15 carbon atoms, the monomer of formula IIis diethylaminoethyl methacrylate which has undergone partial or fullsalinization or quaternization and the monomer of formula III isglycidyl methacrylate.

Preferably the proportion of the monomer of formula I in the copolymeris from about 79% to about 85% by weight, the proportion of the monomerof formula II in the copolymer (in its salt form) is from about 13% toabout 19% by weight and the proportion of the monomer of formula III orIV, or a mixture thereof, in the copolymer is from about 1% to about 5%by weight.

The present invention also relates to an asphaltic material which hasincreased resistance to damage from water, oil and weather, whichmaterial has been treated with a composition which comprises:

(A) from about 0.1 to 4% by weight, on a 100% solids basis, of anaqueous solution or self-dispersed emulsion or dispersion of a copolymerwhich is a reaction product of monomers containing fluorinated groups,cationic groups and nonionic groups, optionally

(B) an effective amount of a penetration assistant, and

(C) water to make up 100%.

The compositions of the present invention are prepared by simplycombining an aqueous solution or self-dispersed emulsion or dispersiontypically containing 20 to 35% by weight of the fluorochemical copolymerand, if desired, the penetration assistant and any conventionaladditives, for example a preservative such as an antimicrobial, abactericide, a fungicide or an algicide, with water of about neutral pHwith gentle agitation. Preferably the compositions are prepared byadding the fluorochemical copolymer and, if desired, the penetrationassistant and any conventional additives to the water. Advantageouslydeionized or distilled water of about neutral pH is employed.

If desired a concentrate of the inventive composition may be prepared bycombining a more concentrated aqueous solution or self-dispersedemulsion or dispersion typically containing 20 to 35% by weight of thefluorochemical copolymer, the penetration assistant and any conventionaladditives and, optionally, none or preferably only a part of the water.The concentrated composition is then diluted with the appropriate amountof water to obtain a suitable concentration of the fluorochemicalcopolymer prior to use in the inventive treatment process.

The compositions of the present invention can be applied to the surfaceof an asphaltic material by any known method, for example by soaking,impregnation, immersion, brushing, rolling or spraying. Advantageouslythe treating compositions of the present invention are applied to thesurface to be protected by spraying, and in particular by spraying witha compressed air sprayer. Suitable spraying equipment is commerciallyavailable.

The amount of the compositions of the present invention to apply to thesurface of an asphaltic material is not critical. The amount should besufficient to thoroughly wet out the surface, but excessive runoffshould be avoided for ecological reasons. Naturally a relatively poroussubstrate, such as a roadway prepared from a mixture of asphalt andrelatively large mineral aggregates, will take up substantially higheramounts of the treating composition due to subsurface penetration whileothers, like asphaltic roofing surfaces will require very little. Afterapplication of the inventive composition to a substrate the treatedsurface should be allowed to thoroughly dry before it is exposed towater or oil.

Interestingly, a porous substrate largely retains its porosity after theinventive treatment, so air and moisture vapor can still pass through.This shows that the surface is not sealed as it would be by aconventional coating. Yet liquid water and oil are strongly repelled asa result of the inventive treatment. The treated substrate also retainsits natural appearance.

The surface of a great variety of asphaltic materials can beadvantageously treated with the inventive compositions. These includeroads and similar asphaltic traffic-bearing surfaces such as driveways,parking areas and airport runways, as well as asphalt compositionshingles and asphalt-coated roofing systems.

Of special interest are roadways and similar asphaltic traffic-bearingsurfaces, especially those that are exposed to freeze-thaw cycles andtreated with salts to melt snow and ice. Treatment of such surfaces withthe compositions of the present invention can greatly mitigatefreeze-thaw damage and thus decrease maintenance and extend the lifetimeof the roadway in a very cost-effective manner.

The effectiveness of the surface treatment by the inventive compositionsis primarily evaluated visually by applying drops of water or motor oil(Pennzoil® 30 weight) to a treated and dried horizontal surface. Whereaswater normally wets out an asphaltic material and forms a continuoussheet or film, or is slowly absorbed by it, depending on its porosity,water is so strongly repelled as a result of the inventive treatmentthat it generally simply forms small, almost hemispherical beads uponthe surface of the treated material. Normally somewhat wider beads whichexhibit a lower contact angle are obtained upon treatment in the absenceof the wetting agent. The water may be left on the treated surface foran indefinite period of time. Eventually it simply evaporates leaving noindication of damage to the surface. Even after extensive freeze-thawcycling, since water doesn't penetrate the treated surface and theadhesion of ice is substantially impaired, there is no evidence ofdamage to the surface.

Motor oil also normally wets out and spreads across an asphalticmaterial and is slowly absorbed by it. However, if the surface of anasphaltic material is treated according to the inventive process thereis substantially less spreading and absorption. Hence even after contactfor an extended period, oil can be readily removed by blotting it upwith an absorbent material or rinsing it off with a stream of water. Thesurface of an asphaltic material treated according to the inventiveprocess shows improved properties relative to the same surface treatedonly with the copolymer.

The following non-limiting examples illustrate the preparation and useof the inventive compositions. However the invention is not limitedthereto. All parts are parts by weight.

Preparation of an inventive composition

To a vessel containing 100 parts of deionized water is gradually addedwith moderate stirring 2.0 parts of LODYNE P-514, an aqueous compositioncomprising about 30% by weight of a cationic fluorochemical copolymerwhich is commercially available from the Consumer Care Division of CibaSpecialty Chemicals Corporation, High Point, N.C., followed by 0.1 partsof Solvent-D, a proprietary liquid which is available from Polypore,Inc., Tucson, Ariz. If desired a compatible preservative or otheradditive is then added and the stirring is continued until the mixtureis visually homogeneous. It is stable on storage.

Application of an inventive composition to a surface

Into a compressed air spraying apparatus is placed a solution having theabove composition. Samples of asphaltic pavement obtained from roadwaydemolition are laid flat on a protected surface and then sprayed withthe inventive composition until their surfaces are thoroughly wet out.Then the treated materials are allowed to thoroughly dry before they areevaluated as described above. The treated materials still exhibitexcellent water and oil repellency after about a year of storage.

Several small sections of asphaltic roadway in Tucson, Arizona aresprayed with the inventive composition as described above. Water stillbeads up on the treated surfaces after almost a year of exposure.

Asphalt composition shingles are laid flat on a protected surface andthen sprayed with the inventive composition as described above untiltheir surfaces are thoroughly wet out. Then the treated materials areallowed to thoroughly dry before they are evaluated. Even after extendedstorage and periodic freeze-thaw cycling, there is no evidence of damageto the surface.

What is claimed is:
 1. A process which provides an asphaltic materialwith increased resistance to damage from water, oil and weather, whichprocess comprises treating said material with an aqueous compositioncontaining:(A) from about 0.1 to 4% by weight on a 100% solids basis ofan aqueous solution or self-dispersed emulsion or dispersion of acopolymer which is a reaction product of monomers containing fluorinatedgroups, cationic groups and nonionic groups, and optionally (B) anamount of a penetration assistant which is effective to increase theability of an aqueous solution or self-dispersed emulsion or dispersionof (A) to penetrate and wet out the asphaltic material, and (C) water tomake up 100%.
 2. A process according to claim 1, wherein the aqueouscomposition comprises from about 0.2 to 2% by weight of the aqueoussolution or self-dispersed emulsion or dispersion of the copolymer on a100% solids basis, and from about 0.01 to 1% by weight of thepenetration assistant.
 3. A process according to claim 1, wherein thecopolymer in (A) is a reaction product of from about 60-90% by weight ofone or more meth(acrylate) monomers containing polyfluorinated alkylgroups, from about 10 to about 40% by weight of one or moremeth(acrylate) monomers containing cationic groups and from about 1 toabout 10% by weight of one or more monomers containing nonionic groups.4. A process according to claim 1, wherein the copolymer in (A) is areaction product of one or more monomers containing nonionic groupsselected from the group consisting of ethylene, propylene, isobutene,chloro-3-isobutene-1, butadiene, isoprene, chloro- anddichloro-butadienes, fluoro- and difluoro-butadienes, vinylidinechloride, vinyl- or vinylidine fluoride, allyl bromide, methallylchloride, vinyl-toluene, alpha-methylstyrene, alpha-cyanomethylstyrene,divinylbenzene, N-vinylcarbazole, methyl vinyl ketone, allyl acetate,allyl propionate, allyl isobutyrate, allyl heptanoate, cetyl vinylether, dodecyl vinyl ether, allyl-, methyl-, ethyl-, propyl-,isopropyl-, butyl-, isobutyl-, hexyl-, heptyl-, ethyl-2-hexyl-,cyclohexyl-, lauryl-, stearyl- or ethoxyethyl esters of acrylic,methacrylic, alpha-chloroacrylic, crotonic, maleic, fumaric, itaconic,citraconic and senecioic acid, glycol or polyalkyleneglycol diacrylatesand dimethacrylates, acrylonitrile, methacrylonitrile,chloro-2-acrylonitrile, cyano-2-ethyl acrylate, methyleneglutaronitrile, vinylidene cyanate, isopropyl cyanoacrylate,trisacryloyl-hexahydro-s-triazine, allyl alcohol, allyl glycolate,isobutenediol, allyloxy-ethanol, o-allylphenol, divinylcarbinol,glycerol-allyl ether, acrylamide, methacrylamide, maleamide andmaleimide, N-(cyanoethyl)acrylamide, N-isopropyl-acrylamide,diacetone-acrylamide, N-(hydroxymethyl)-acrylamide and methacrylamide,N-(alkoxymethyl)-acrylamides and methacrylamides,glyoxal-bis-acrylamide, amino-3-crotononitrile, monoallylamine,vinylpyridines, glycidyl acrylate or methacrylate and theirchlorohydrins, allyl glycidyl ether and acrolein.
 5. A process accordingto claim 4, wherein the nonionic monomer comprises at least one monomerselected from the group consisting of glycidyl acrylate or methacrylateand their chlorohydrins.
 6. A process according to claim 1, wherein thecopolymer in (A) is a reaction product of monomers copolymerized in thefollowing percentages by weight, relative to the total weight of thecopolymers:(a) from about 60% to about 90% of at least one monomer ofthe formula I:

    R.sub.f --Q--A--C(O)----C(R)═CH.sub.2                  (I)

wherein R_(f) is a straight or branched-chain perfluoroalkyl group offrom 2 to about 20 carbon atoms, R is H or CH₃, A is O, S, or N(R'),wherein R' is H or an alkyl of from 1 to 4 carbon atoms, Q is alkyleneof 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbonatoms, --(C_(n) H_(2n))(OC_(q) H_(2q))_(m) --, --SO₂ --NR'(C_(n)H_(2n))--, or --CONR'(C_(n) H_(2n))--, wherein R' is H or an alkyl of 1to 4 carbon atoms, n is 1 to 15, q is 2 to 4, and m is 1 to 15; (b) fromabout 10 to about 40% of at least one monomer of the formula II:

    (R.sub.1).sub.2 N--CH.sub.2 CH.sub.2 --O--C(O)--C(R.sub.2)═CH.sub.2 (II)

wherein R₁ is an alkyl group of from 1 to 3 carbon atoms, R₂ is H or analkyl radical of 1 to 4 carbon atoms, and wherein the nitrogen is 40 to100% quaternized or in the form of a salt; and (c) from about 1 to about7% of at least one monomer of formula III or IV, or a mixture thereof:##STR3## or

    Cl--CH.sub.2 --CH(OH)CH.sub.2 --O--C(O)----C(R.sub.4)═CH.sub.2 (IV),

wherein R₃ and R₄ are each independently H or the same or differentalkyl radical of 1 to about 4 carbon atoms.
 7. A process according toclaim 6, wherein R_(f) is a straight chain perfluoroalkyl group of 2 toabout 20 carbon atoms, or a mixture thereof, A is O and Q is an alkyleneof 1 to about 15 carbon atoms, the monomer of formula II isdiethylaminoethyl methacrylate which has undergone partial or fullsalinization or quaternization and the monomer of formula III isglycidyl methacrylate.
 8. A process according to claim 6, wherein theproportion of the monomer of formula I in the copolymer is from about79% to about 85% by weight, the proportion of the monomer of formula IIin the copolymer (in its salt form) is from about 13% to about 19% byweight and the proportion of the monomer of formula III or IV, or amixture thereof, in the copolymer is from about 1% to about 5% byweight.
 9. A process according to claim 1, wherein the aqueouscomposition is sprayed onto the surface of the asphaltic material with acompressed air sprayer.
 10. A process according to claim 6, wherein theaqueous composition is sprayed onto the surface of the asphalticmaterial with a compressed air sprayer.
 11. A process according to claim1, wherein the asphaltic material is an asphaltic traffic-bearingsurface, asphalt composition shingles or an asphalt-coated roofingsystem.